JPS59174839A - Silver halide color photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide color photosensitive material having superior solubility and dispersion stability and color developability by incorporating a specified yellow coupler. CONSTITUTION:A silver halide color photosensitive material contains in at least one layer a yellow coupler represented by the formula shown here in which R1 is tertiary alkyl or aryl; R2 is halogen or alkoxy; R3 is H, halogen, alkoxy, alkyl, or carbonamido, preferably, H, halogen, or alkoxy; R4 is alkyl or alkenyl; R5 is nitro, cyano, carboxy, sulfo, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, acyl, alkylsulfonyl; arylsulfonyl; alkoxysulfonyl, or sulfamoyl, preferably, nitro, carboxy, alkylsuofonyl, or the like; and R6 is H, halogen, alkyl, alkoxy, carboxy, nitro, or alkoxycarbonyl.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a silver halide color photographic light-sensitive material containing a two-equivalent cross-colored coupler with improved dispersion stability and color development.

It is well known that after a silver halide photographic material is exposed to light, an oxidized aromatic primary amine developer and a dye-forming coupler react to form a color image. In this method, a subtractive color reproduction method is usually applied, and red,
Cyan, magenta, and yellow color images, which are complementary colors to green and blue, are formed. The reaction between the coupler and the oxidation product of the color developing agent takes place at the active site of the coupler, and couplers having a hydrogen atom at the active site are equivalent couplers, i.e. they are theoretically stoichiometric to form one mole of dye. In general, a large amount of silver halide having development nuclei is required as an oxidizing agent. On the other hand, those having an anionic leaving group at the active site are 2-equivalent couplers, i.e. couplers that require only 2 moles of silver halide with development nuclei to form 1 mole of dye; Compared to the equivalent cazolers, the amount of silver halide in the photosensitive layer can generally be reduced and the film thickness can be made thinner, making it possible to shorten the processing time of the photosensitive material and sharpening the color image formed. degree will improve. Furthermore, the coupling activity of two-equivalent couplers with color developing agents can be varied widely depending on the nature of the leaving group.

Furthermore, two-equivalent couplers whose separation products have the effect of inhibiting development are development inhibitor-releasing couplers (D
It is called an IR coupler and suppresses development in proportion to the amount of developed silver, so it has effects such as fine graining of images, adjustment of two gradations, and improvement of color reproducibility. It can also be used in a diffusion transfer method by utilizing the effect on adjacent layers.

It is also possible to use it in a diffusion transfer method in which the leaving group contains a diffusible dye moiety and the leaving group is used to form a dye image of the diffusible dye on the image-receiving layer.

This type of coupler is called a diffusible dye-releasing coupler.

Also some kind of colored. A two-color coupler has a masking effect for color correction of a one-dye image, and this type of coupler is called a colored coupler.

In this way, various functions can be imparted to the 2-equivalent coupler by selecting the leaving group.

Incidentally, in recent years, there has been a strong demand for higher sensitivity and higher image quality in silver halide photographic materials.

Therefore, especially for yellow couplers, it is desired to develop a coupler that can be stably dispersed using a small amount of a high-boiling organic solvent for dispersion and that can provide high color density upon development. Hitherto, in order to achieve this objective, studies have been made on leaving groups as yellow 2-equivalent couplers or on diffusion-blocking groups called so-called palast groups. For example, as #degrouping, US Patent 3. ≠Or, /7
≠ and 3. 33. ! 0/@ has an aryloxy group, and U.S. Pat.
2-≠! /3T has an imido group, JP-A-Sho! /-/7≠
No. 3g has a triazolyl group, JP-A-Sho t / - / +
J--2'/R number has a tetrazolyl group.

Japanese Patent Publication No. 12-33J and 0-341232
Benzo), IJ, and azolyl groups have been proposed in US Pat. ri μ/, tO1
No. 2-cyclo means ≠- and one-butylphenoxy group, West German Patent (OLS) J, 9/! , No. 023, an alkoxyalkyl sulfonamide group is used in U.S. Pat. Ri33,! ; No. 01 is an alkyl or arylsulfonamide group.

The alkoxyalkylcarbonamide group and the alkoxyalkylcarbonamide group are
The number contains an alkylsulfonyl group, as described in JP-A-57-7-53.
There is a sulfamide group in the r number,
No. 1, respectively, discloses mono-substituted sulfonamide groups. however.

Many of these have insufficient coupling reactivity, poor dispersibility, which causes coating failures, and low solubility in high-boiling organic solvents.

It has drawbacks such as low storage stability when made into an emulsion, and is not necessarily satisfactory.

An object of the present invention is to provide a color photographic material containing a yellow 2-equivalent coupler having excellent solubility and 1-dispersion stability.

Another object of the present invention is to provide a color photographic material containing a yellow 2-equivalent coupler with excellent color development.

Another object of the present invention is to provide a yellow 2-equivalent coupler whose photographic properties are not affected by changes in the amount of high-boiling organic solvent used for protection dispersion.

As a result of extensive research conducted to achieve the above objects, we have found that these objects of the present invention can be achieved by a yellow 2 monovalent coupler represented by the following general formula (I).

General formula (1) In the formula, R1 represents a tertiary alkyl group or an aryl group.

R2 represents a halogen atom or an alkoxy group, R3 represents a hydrogen atom, a halogen atom, an alkoxy group, an alkyl group or a carbonamide group, and 4 represents an alkyl group or an alkenyl group. R5 is a nitro group, cyano group, carboxy group, sulfo group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, acyl group, alkylsulfonyl group, arylsulfonyl group, alkoxysulfonyl group, or sulfamoyl group, and R6 is hydrogen atom.

Represents a halogen atom, an alkyl group, an alkoxy group, a carboxy group, a nitro group, or an alkoxycarbonyl group.

By the way, the British patent/, θ77, Za7μ issue has Yellow 2.
A yellow coupler is suggested which has an alkylsulfonyl group disubstituted and an aryloxy leaving group at the 3- and 5-positions of the anilino nucleus of the equivalent coupler.

A reduction in the film thickness of the emulsion layer due to -2 emulsion weighting is advocated.

On the other hand, Japanese Patent Application Laid-open No. Sho JRJ-93/TA 3 discloses a yellow coupler having an alkoxycarbonyl substituted with a carbamoyl group, a diffusion inhibiting group having l-, and an aryloxy leaving group. In the issue, couplers having an aryloxy leaving group and an aryloxycarbonyl group are disclosed as compound examples, and both of them are capable of producing sufficient dye images even when processed with a color developing solution containing a reduced amount of benzyl alcohol. What you get: 1. It is said to have good image storage stability. However, these compounds have drawbacks such as poor dye image storage stability and inability to obtain a sufficient dye image when the amount of high-boiling organic solvent for dispersion is reduced. The advantages of the present invention will be made clear in the examples herein.

Next, general formula (I) will be explained in detail.

In general formula (1), as the tertiary alkyl group or aryl group for R1, those known for yellow couplers can be used. Yoshitang Shikke 31J), 1 as an alkyl group
+, butyl group, and adamantyl group, and examples of the aryl group include phenyl group, ≠-methquinphenyl group, α-methylphenyl group, and α-acetamidophenyl group.

In addition to the benzene nucleus di(halkyl ester group or haalkenyl ester group) of the anilino moiety of general formula (I), at least a halogen atom (fluorine, chlorine, bromine, etc.) or an alkoxy group (preferably is a carbon number/~2.2.

For example, either one of a metquin group or an etquin group) is substituted. In addition to these, halogen atoms (same as above), alkoxy groups (same as above), and alkyl groups (preferably those having 7 to 22 carbon atoms, such as methyl and ethyl groups) are included in the definition of R3.

A carbonamide group (preferably one having 2 to 22 carbon atoms, such as an acetamido group or a benzamide group) may be substituted. Note that R3 is more preferably a hydrogen atom, a halogen atom, or an alkoxy group.

In general formula (I), R4 of the ester group that is substituted with only one benzene nucleus of the anilino moiety is an alkyl group or an alkenyl group, and these may be linear or branched, and the number of carbon atoms is /~, 2≠ is preferred. In addition, in the coupler of the present invention, it is preferable to use this moiety as a palust group, so R4
J-21A is more suitable as the number of carbon atoms. Specific examples of R4 include (fin-hexyl ahn-octyl group,
n-dodecyl group, n-tetradecyl group, n-hexadecyl group, n-tetradecyl group, 2-hequinrudecyl group.

Examples include ta, 7.7-dolimethyl-λ-(/,3.3-)limethylbutyl)octyl group, α-ethylhexyl group, 2-octyldodecyl group, oleyl group, -terf-cenyl group, and ni-hebutadecenyl group. .

In general formula (I), at least one substituent (R5) is present on the benzene ring of the aryloxy leaving group.

In addition to a nitro group, an ano group, a carboxyne group, and a sulfo group, R5 is preferably an arylsulfonyl group having 2 to 23 carbon atoms (e.g., a methoxycarbonyl group, an ethoxysulfonyl group), preferably -] 1 = carbon number 7-23 aryloxycarbonyl group (e.g. phenoxycarbonyl group),
Preferably a carbamoyl group having 2 to 23 carbon atoms (eg, dotesylcarbamoyl group), preferably an acyl group having 2 to 22 carbon atoms (eg, acetyl group, benzoyl group).

Preferably, an alkylsulfonyl group having carbon number/~22 (
? lLt hamethanesulfonyl group, ethanesulfonyl group)
, preferably carbon number ~-! μ arylsulfonyl group (?Lt habenzenesulfonyl & benzenesulfonyl group with ft-substituted hydroxy group, halogen atom, alkyl group, or aralkyloxy group at the 4' position), preferably an alkoxysulfonyl group with carbon number/~22 (e.g. ethoxysulfonyl group), preferably a sulfamoyl group having 1 to 22 carbon atoms (e.g. evadimethylsulfamoyl group, phenylsulfamoyl group, 0-tetradecyloxyphenylsulfamoyl group) . More preferred R5 is a nitro group, a carboxyne group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group.

Aryloxy leaving groups include, in addition to R5, nitro groups, carbonyl groups, alkoxycarbonyl groups (
(same meaning as above), preferably an alkyl group (e.g. methyl group, ethyl group) having a carbon number/~2.2, preferably a carbon number/
~,! 2 may be substituted with an alkoxy group (eg, methoxy group, ethoxy group) or a halogen atom (fluorine, chlorine, bromine).

Specific examples of the -ruoxy leaving group in general formula (I) are shown below.

Next, specific examples of the yellow λ equivalent coupler represented by the general formula (I) of the present invention will be shown.

(1) (2) 02 H (3) (4) O2 (5) 0C14H29-n (6) 02 0)-! (7) Ha OOH (9) OH (11) 802N(CH3)2 02 (13) 02 1-T The coupler of the present invention is synthesized from ≠ equivalent couplers by a reaction as shown in the following general formula, for example.

(X=Br, α) In the case of bromination (A), for example, bromine.

-By using bromosuccinimide etc., x y
In the case of 'c chlorination, a halide can be obtained in high yield by using, for example, sulfurylchloride chloride. In this case the reaction solvent and tecichloromethane,
It is preferable to carry out the reaction in a halogenated solvent such as chloroform, dichloroethane, etc. In reaction (B), a halide and phenol are induced: methylene chloride, chloroform, xylethane, acetonitrile, dimethylformate, dimethylacetamide, etc. in the presence of a base. , tetrahydrofuran.

- By reacting in a solvent such as xane, the desired coupler can be obtained in high yield. In this case, the bases are sodium hydroxide, potassium hydroxide, sodium carbonate, and sodium methoxide.

Triethylamine, N-ethylpiperidine, N-ethylmorpholine, /, /, 3,3-tetraamino guanidine, pyridine, DBU, 1) BN.

+] ABco etc. can be used.

Phenols may be used in the reaction as alkali metal salts. Examples of synthesis of the compounds of the present invention are shown below.

Synthesis Example 1 Synthesis of Compound Example (1) α-pivaloyl-2-,chloro-! -For the reaction between dodecyloxycarbonylacetanilide and odor
α-promo α-pivaloyl-,2-ri.

rotardodecyloxycarbonylacetanilide and/or t9 and acetonitrile, dissolved in Oml, pencil-hydroxybenzoate, dimethylformamide, dissolved in OmQ, triethylamine, 2j
The mixture was added to the mixture containing rr+Q and reacted at room temperature for 2 hours.

The reaction mixture is mixed with caustic soda and water.
! Ethyl acetate poured into an aqueous solution of! Extracted with 00mQ.

The ethyl acetate solution layer was separated, washed with a 3% aqueous hydrochloric acid solution, and dried with water-washed salt.

Ethyl acetate was distilled off under reduced pressure to obtain 2 oils. This oil was dissolved in acetic acid ester for 2 nights θmQ, 10% palladium carbon 79 was added, hydrogen pressure≠θ~/cm I reaction temperature so 0cio, and the reaction was carried out for reductive decomposition.
The catalyst, ξ radium carbon, was cooled, ethyl acetate was distilled off under reduced pressure, and the residue was recrystallized with methanol to give soybean.
The desired compound was obtained. The melting point was //l, ~/17.

Elemental analysis value: CHN Actual measurement: tj, 77 7. Gua 2. Tata calculation value tj
,! 3 7.3/ 32 Synthesis Example 2. Compound example (2
) Synthesis of α-chloro-α-pivaloyl-1-methoxy-tertetradecyloxycarbonylacetanilide obtained by the reaction of α-pivaloyl-2-methoxy-j-tetradecyloxycarbonylacetanilide with sulfuryl chloride/
309 to acetonide 1) 300m1! Dissolved in p,
≠'Dihydroxydiphenyl sulfone 300? dimethylformamide 4t00 m11. Triethylamineta OmQ was added dropwise to the reaction solution heated to A5-70, and reacted for 7 hours.

The reaction mixture was poured into a water bath of 1002 nV of caustic soda and extracted with 200 mQ of ethyl acetate.

The ethyl acetate solution layer was separated, washed with a 3% aqueous hydrochloric acid solution, washed with water, and dried over sodium sulfate.

Ethyl acetate was distilled off under reduced pressure, and the residue was dissolved in hexane (300ml).
．． , Improper Tools/00 m11. The target compound 7090 was obtained by recrystallization with a mixed solvent of . Melting point: 3-9
It was j0C.

Elemental analysis value: CHN Actual value: 6, 12 7. tj /, 7 ta calculated value t
t, 7j 7.4# /, 19 Synthesis Example 35 Synthesis of Exemplified Compound (3) α-Chloro-α-obtained by the reaction of α-piparoyl-cochlorotadodecyloxylponylacetanilide and sulfuryl chloride Pivaloyl-2-chloro-! −)
'509 of tacyloxylponylacetanilide and 200 mQ of acetonitrile.

The solution was added to a solution of p, l hydroxydiphenyl sulfone/2 t dissolved in 100 mD of dimethylformamide, and the mixture was heated and stirred at 70 to 0°C. Triethylamine/♂mQ was added dropwise to this, and the mixture was reacted for 2 hours.

The reaction mixture was mixed with 10% caustic soda. ,water! Pour into 00mQ aqueous solution and add ethyl acetate! Extracted at 00 mD.

Separate the ethyl acetate layer and wash with 3% aqueous hydrochloric acid.

After washing with water, it was dried with Glauber's salt. Ethyl acetate was distilled off under reduced pressure, and the residue was diluted with hexane (1100 rnQ) and isopronominol (10 rnQ).
Recrystallization was performed using a mixed solvent of 0mQ to obtain the target compound of 0mQ. The melting point was ~73°C.

Elemental analysis value (CH) CHN Actual value tj, II t, 7r /, PI calculated value
Otsu 3. ri/Otsu, 7. ! /, 26 Synthesis Example 41 Synthesis of Exemplified Compound (6) α-Biparoyluco, l/l-dichloro-5-[(2-
α-chloro-α- obtained by the reaction of hexyl)thenyloxycarbonyl]acetanilide with sulfuryl chloride
Viparoyluco, Gooji Chloro! Resistance to CC2-hexyl) tethyloxycarbonyl acetanilide t/9 to acetonitrile/00 mQ.

Dissolve μ, 44' dihydroxydiphenyl sulfone/702 in 300 mQ of dimethylformamide.
Add it to what is dissolved in it! It was heated to 0~zO0C.

30 mQ of triethylamine was added dropwise to the reaction solution, and the reaction was stirred for 3 C minutes. The reaction mixture was mixed with caustic rot and water.
Pour into 00mQ aqueous solution.

Extraction was performed with ethyl acetate ♂θOmO. The ethyl acetate solution layer was separated, washed with a 3% aqueous hydrochloric acid solution, washed with water, and dried over sodium sulfate.

Ethyl acetate was distilled off under reduced pressure, and the residue was diluted with hexane (10,100 ml).
Recrystallization with O gave the desired product≠02. The melting point was 77-70C.

Elemental analysis value CHN Actual measurement value t2. t≠ t, ri/ /, 72 calculated value t
2. t♂ Otsu, ♂ta /, 72 Among the color photographic materials containing the coupler of the present invention, for example, DIR coupler and D
IR compounds (for example, U.S. Patent No. 3.
3,227°! RJ No. 3,377.527 JP-A-12233, No. 0-311232,
1. Known yellow dye-forming couplers other than those of the present invention (for example, West German Patent Application (OL8) 2.,!/3, ≠t1, U.S. Pat. No. 3, E.10) , No. 30, 3. A≠≠, μg No. 7.

39g9≠, those described in No. 17jr), magenta dye-forming couplers (for example, U.S. Patent No. 3.O/j, !06)
No., West German Patent Application (OL8) 2, 4L/D, Tata No. 7, OL8, 4'2'A, ≠67, etc.), cyan dye-forming couplers (e.g., U.S. Pat. , 4174t, 2!73, 3,03≠, ♂ri 2, 3.Tata/, 313, 3゜3//, '/-7, 3.≠74.T3 (as stated in the No. 1) may be included.

The couplers of the invention are conveniently dispersed in photographic emulsions as solutions in organic solvents. Specific examples of methods for dispersing couplers are described in detail in US Pat. No. 3,1,7t, 137. Organic solvents useful for dissolving couplers include those that are sparingly soluble in water and have an oblate boiling point, such as substituted hydrocarbons, carboxylic acid esters, benzoic acid esters, citric acid esters and carboxylic acid amides, These include phosphoric acid esters and ethers. Specific examples include di-n-butyl phthalate, n-octyl benzoate, O-acetyltributyl citrate, tricresyl phosphate, tri-n-hexyl phosphate,
N,N-diethylcaprylamide and the like. In addition to these high-temperature solvents, it is advantageous to use low-boiling auxiliary solvents to aid in dissolving the coupler. Examples include propylene carbonate, ethyl acetate, butyl acetate, cyclohexanol, tetrahydrofuran, cyclohexanone, and the like.

The yellow 2-equivalent coupler of the present invention exhibits constant performance even when the amount of the high-boiling solvent changes, so the ratio of the solvent to the coupler can be varied over a wide range. ratio) -3:/-0:/, especially l:/
The following ranges are suitable.

It is advantageous to use surfactants to help finely disperse these solvents in the hydrophilic colloids used in photographic emulsions. / Diffusion-resistant couplers having a pallast group and a carboxylic acid group or a sulfonic acid group in the molecule are soluble in neutral to weakly alkaline aqueous solutions. The aqueous solution can be added to the photographic emulsion.

The amount of coupler used is generally 5 to 7 moles of silver halide.
/ Evening 00? Although it is used as an additive, it can be changed depending on various application purposes, and preferably 10 to 000f per mole of silver halide! is the amount added.

The coupler of the present invention can be used in various silver halide sensitive materials.

For example, it can be used for various color sensitive materials such as color negative film, color positive film, color reversal film, and color one-permanent film, but it is particularly preferable to use it for color reversal film and color paper.

The couplers of the present invention can be used in combination with multilayer color photosensitive materials (e.g., U.S. Pat. No. 3,721., A11).

Same 3. ．． f/l, No. 13/, British Patent III, 41
R7, Fukoku patent! It can be applied to the method described in P23,011, etc.) or the method described in JP-A-Shoyu θ-j, /7, and also in West German Patent Application (OLS), 2,
322. / may also be applied in combination with the DIR compounds described in No. 5 or US Pat. No. 3,703.37.

The light-sensitive material used in the present invention may contain a pi blue-converted phenol derivative, such as an hydroquinone derivative, in the emulsion layer or a layer adjacent thereto. This is advantageous for the stability of the color image. Particularly effective p-substituted phenol derivatives are described in U.S. Patent λ, 31.0.290, 2. t/r,
A11, 2. t7jf, No. 31II, 2,710,1
0/No., , 2,721, A37 No., 2,732, 3θ
No. 0, No. 2,733.76r, No. 2.1/l, No. 021,
3. Hiro! No. 7,07, 3. Otori, No. 262 S Tokuko Sukyu 3-/3. μ Riwo issue: US Patent No. 2,73! ;.

Vt1, Japanese Unexamined Patent Publication No. 7-G, No. 73, U.S. Patent No. 3.
No. 1132.300, No. 3,373,012, No. 3.
This is what is described in 7th Edition, No. 427, 3rd, 7th Edition, and No. 337.

Sensitive materials containing couplers of the present invention may be used in emulsion layers or adjacent layers for image stabilization, such as in US Pat. No. 3,2! θ,
Otsu No. 17, No. 3. ．． 2j3. It may also contain an ultraviolet absorber as described in No. 2/.

The coupler according to the present invention can also be used in low-silver-containing light-sensitive materials in which the silver halide in the emulsion is one to one hundredth of that of conventional light-sensitive materials. For color sensitive materials with a reduced amount of silver halide in this way, / Me oxide, cobalt complex salt, or sodium chlorite is used [an image forming method that increases the amount of produced dye by using color intensification] (for example, West German patent publication (OLS) 2
No. 337.49μ, U.S. Patent 3. t711. ≠RI No. 0, 3.76/, 21, 5, West German Patent Publication (OLS
), 2.01/-IA, No. 133, 2.0ri 6133
No. 9, same, z, ort, 31r (No. 1, same 2.2
2A.

No. 770, JP-A No. 4TF-4, 7, 2r, IAf-
A sufficient color image can be obtained by using the following methods.

To color develop a photosensitive material containing the coupler of the present invention,
This can be done by a conventionally known general method. That is, a dye image and a silver image are produced by color development using substituted p-phenylenediamine.

A subsequent bleaching bath oxidizes it to silver salts, and a fixing bath dissolves and removes the remaining silver salts, leaving only the dye image. In this case, it is carried out in combination with a pre-hardening bath, a neutralization tower, a fifth developing bath, an image stabilizing bath, etc., if necessary.

Many conventionally known compounds can be used as p-phenylenediamine derivatives for developing the color photosensitive material according to the present invention. A particularly useful p-phenylenediamine color developer is an N,N-difurkyl-p-phenylenediamine compound, and the alkyl group and phenyl group may be substituted or unsubstituted. Among them, an example of a particularly useful compound is N
.

N-diethyl-p-phenylenediamine! acid salt.

N-methyl-p-phenylenediamine hydrochloride, N.

N-dimethyl-p-phenylenediamine hydrochloride.

2-amino-ter(N-ethyl-N-dodecylamino)
-Toluene, N-ethyl-N-(β-methanesulfonamidoethyl-3-methyl-Hiro-aminoaniline sulfate,
N-ethyl-N-β-hydroxyethylaminoaniline, lA-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-1)-)luenesulfonate, N,N-diethyl-3- Methyl-7-aminoaniline.

Examples include N-ethyl-N-(β-hydroxyethyl)-3-methyl-Hiro-aminoaniline.

Examples of bleaching agents include persulfate monodichromate, red blood salt, hydrogen peroxide, and ferric ion complex salts. Ferric ion complex salts are complexes of ferric ions and chelating agents such as aminopolycarboxylic acids, aminophosphonic acids, or salts thereof.

Aminopolycarbonate salt or aminopolyphosphonate is an alkali metal or ammonium salt of aminopolycarboxylic acid or aminopolyphosphonic acid.

It is a salt with a water-soluble amine. The ferric ion complex salt may be used in the form of a complex salt, and ferric salts 1 such as ferric nitrate,
An m2 iron ion complex salt is formed in a solution using ferric chloride, ferric sulfate, ferric ammonium nitrate, ferric phosphate, etc., and a chelating agent such as aminopolycarboxylic acid or aminopolyphosphonic acid. Good too.

As fixing agents, thiosulfates (e.g. ammonium thiosulfate, thio(j[sodium, thioljMH potassium, etc.), thiocyanates (e.g. ammonium thiocyanate, sodium thiocyanate, potassium thiocyanate, etc.) + 3+'-dithia- /.

Examples include thioether compounds such as male-octanediol. However, these can be used in one batch or by mixing two or more of them.

The yellow binary coupler of the present invention has excellent solubility even in small amounts of high-boiling solvents, and has high storage stability when made into an emulsion. It also shows relatively constant performance even when the amount of high boiling point solvent is varied. Furthermore, it provides excellent color development and high gradation, and has extremely good light resistance, making it very useful.

The present invention will be explained in more detail with reference to Examples below. The comparative couplers used in each example were the following yellow couplers C-/ and C-2 described in U.S. Pat. yellow coupler C-3 similar to that; yellow coupler C-≠ described in JP-A No. 54-/JR/932: Akira Mochihisa st-≠
Yellow coupler c-s similar to jt/3J'; JP-A-5
Yellow coupler c- described in Tata 3/j No. 3,
g; yellow coupler C-7 suggested in British Patent No. 077.8'7≠;
This is the yellow coupler C-g described in No.

C-/(Comparison in Examples 1 and 2.5) 0OI-1 C-3 (Comparison in Examples 2 and 4) C-1/- (Comparison in Examples 4 and 5) C-! (Comparison in Example 3) C2H5 cm, g (Comparison in Example 3) COO, E-1 cmf (Comparison with Examples 4 and 5) α α Example Coupler of the present invention (11 to (14 and Comparison coupler C
Emulsions A to P of -/, C-, 2 were obtained by heating and dissolving the following oil phase and water phase, respectively, mixing them, and emulsifying them with a homo blender.

(Oil phase) Coupler of the present invention or comparative coupler 109 tricresyl fluoride) /F ethyl acetate
/ j cc (aqueous phase) Sodium dodecylbenzenesulfonate 0.7? gelatin
lS9 water
/! Occ these A-
After storing the emulsion of P in a refrigerator at 7 °C for 1 day,
Heat to 00C to dissolve.

/ 00 cc of hot water was added and held at this temperature for +y hours. Thereafter, these emulsions were filtered under reduced pressure using a Millipore EC filter to examine filtration suitability.

A to N prepared using the couplers of the present invention could be easily filtered without clogging, and no residue remained on the filter.

In contrast, emulsions prepared using comparative couplers 0
．． In PK, solid matter was formed and clogging was severe, and only a small amount of the emulsion could be completely filtered.

From the above results, it can be seen that the coupler of the present invention has excellent solubility compared to the comparative coupler even if the amount of high-boiling organic solvent is slightly reduced, and furthermore, when made into an emulsion using this solution, the storage stability is extremely good. .

Example 2 In order to evaluate the effectiveness of the inventive couplers, one inventive and comparative coupler was coated with tricresyl phosphate (see Table 1) on a triacetylcellulose support provided with an undercoat layer. (The amount was varied as shown)
and dissolved in ethyl acetate.

Samples 20/-20 were prepared by coating an emulsion layer as described below which was added by emulsifying and dispersing it in an aqueous gelatin solution. The coating amount of each substance is shown in parentheses as 97 m or m Ot/m .

(1) Emulsion layer Negative silver iodobromide emulsion (grain size -'0x10-3 mo) 7m2) Invention and comparative couplers (/, /X/0'3m02/m2) Tricresyl phosphate (Table/ ) Gelatin (2,3W/m2) (2)
Protective layer λ, ≠-dichloro-t-hydroquine-s-triazine sodium salt (o, osq/m”)
Gelatin (3/7 m2) These coated samples were subjected to primary color 5-image processing using white light for sensitometry. The density of the processed sample was measured under blue light to obtain photographic data. The photographic data obtained are shown in Table 1.

The phenomenon processing used here was performed at 3f 0c as follows.

1. Color development・・・・・・・・・・・・・・・
・3 minutes, 2 seconds, bleaching...
...6 minutes 30 seconds 3, wash with water...
・・・・・・・・・3 minutes/evening seconds 4, constant...
・・・・・・・・・・・・・・・ for 30 seconds 5, wash with water ・・・・・・・・・・・・・・・ 3 minutes/j seconds 6,
Stable・・・・・・・・・・・・・・・3 minutes/
The composition of the treatment liquid used in each step is as follows.

Color developer sodium nitrilotriacetate /, O? Sodium sulfite g, θ? sodium carbonate
30. Of/potassium bromide
/ , 4t@hydroxylamine sulfate , :Z, ll-9≠-(N-ethyl-N-
βhydroxyethylamino)-2-methyl-anilinosulfate ≠, j? Add water / l bleach solution ammonium bromide l 0.09 ammonia water (21%) 2! r, OmQ ethylenediamine-tetraacetic acid sodium iron salt /3θ 2-glacial acetic acid
/l1mQ add water
/ Fixer Sodium Tetrapolyphosphate 2.02 Sodium Sulfite ≠, Of Ammonium Thiosulfate (70 Articles) / 7J, Oml! Sodium binitrate
≠, add 7f water
It stabilizer 7 g, Om
Q Calorie the water ′ l 1st
As is clear from the table, when the amount of tricresyl phosphate used is reduced, yellow 2-equivalent Cabjie C-i, c-, z and C-3, which have a different structure of anilino moieties than the present invention, softened greatly by 13. On the other hand, the Yellow 2 mass coupler of the present invention shows less dependence of color development on the amount of tricresyl phosphate, and has higher sensitivity and harder filter gradation than the comparative coupler under any conditions. I understand.

Example 3 Couplers of the present invention (21?
Q) to prepare samples 30/-30j. This sample was exposed to light and developed in the same manner as in Example 2 to prepare strips for a photobleaching test.

The developed strips were exposed to a xenon photobleaching tester (100,000 lux) manufactured by Atlas Corporation in the United States for 4 t♂ hours. Although the dye images formed with the aryloxy separation yellow 2-equivalent coupler C-J and the aryloxy separation yellow 2-equivalent coupler C-7 in which the benzene nucleus of the anilino moiety is substituted with two ester groups have poor light resistance. Comparatively, the dye images formed with yellow of the present invention and 2- and 2-2 have higher light resistance than the comparative samples.

Example 4 K on cellulose triacetate film support.

A multilayer color light-sensitive material≠Ol was prepared, each layer having the composition shown below.

(Sample ≠O7) 1st layer: antihalation layer (AHL) gelatin layer containing black colloidal silver λ layer: intermediate layer (ML) gelatin layer containing an emulsified dispersion of t-octylhydroquinone 3rd layer: 1st red-sensitive emulsion layer (RLI) /, 7li9/m2 Sensitizing dye ■...Axlo per mole of silver
Molar sensitizing dye ■・・・1, j′xl per 1 mole of silver
O mole coupler EX-/...O0O per mole of silver
≠Molar coupler E゛X-2... Group 0.00 for 81 moles
3 mole coupler EX-3... group @ θ, ooo for 7 moles
t mol ≠ layer: 2nd red-sensitive emulsion layer (R, L2) 1, ≠ 2/m2 Sensitizing dye I: 3% per mol of silver 10
Molar sensitizing dye■・・・・・・For 1 mole of silver/, 2Z1
0 mole coupler EX-≠・・・0.0 per mole of silver
2 mole coupler EX, z... mark, o, ooi for 1 mole of silver
6 mole competitive compound EX-ta...0.003 per mole of silver
Mol sth layer: Intermediate layer (ML) Same layer as the 2nd layer: 1st green-sensitive emulsion layer (GLI) 1, 2/m2 Sensitizing dye ■・・・・・・For 1 mol of silver 3×10
Molar sensitizing dye■...For 1 mole of scissors/×IO/mole coupler EX-&...For 1 mole of pot for O,OS molar coupler EX-7...1 for 1 mole of silver Against o, ooi
Molar coupler EX-3...0.0 per mole of silver
0/! r mole 7th layer: second green-sensitive emulsion layer (GL2) / , 49/(H2 Sensitizing dye ■...... λ, !'X1 for 1 mole of silver
0 mole sensitizing dye ■ Old... 0 for 1 mole of silver, r'X10-5 mole coupler EX-f...0.0 for 1 mole of silver
/Tamol 1st r layer: Yellow filter single layer (Y11i'L) A gelatin layer containing yellow colloidal silver and an emulsified dispersion of 2,5-di-t-octylhydroquinone in an aqueous gelatin solution.

1st layer: 1st blue-sensitive emulsion layer (BLI) /,! p/1η2 Coupler C-≠...0.2r mole per mole of silver Coupler EX-30,0/Tamol 10th layer: Second blue-sensitive emulsion layer (BL2) /, /9/(y12 Coupler C -≠・・・・・・o, oA per mole of silver
Molar 1st/layer: Fine grain emulsion that is not chemically sensitized (grain size 0.0AB 1 mol silver iodobromide emulsion) 0,397
m2 UV absorber EX-5'...0.
197m2 EX-'/ 0-...-0
, 29 / m2 12th layer: gelatin / , 0? /m2
Formaldehyde scavenger EX-//0,! r?
7m2 hardener EX −/J O, −
i! The coated sample prepared as above with S'/rn2 was designated as '/-0/.

(Samples 4t02, μ03) Same as above, except that the couplers C-Hiroshi of the second and 10j- of sample G O/ were changed to the couplers (3) and (8) of the present invention.
Samples 1702 and 4t03 were prepared in the same manner as in i.

After these samples were left at 1I-Q0C relative humidity of 70% for 4 hours, image quiz double light was applied and the same treatment as in Example 2 was performed. Concentration was measured using blue light. The results obtained are shown in Table 3.

As is clear from Table 3, yellow 2-equivalent couplers C-≠, c-, r,
and Yellow 2 whose anilino moiety structure is different from that of the present invention.
Equivalent coupler C-,? It can be seen that the yellow 2-equivalent coupler of the present invention exhibits high sensitivity and high gradation in both cases.

Compound Sensitizing Dye I Used to Prepare Samples of Example 4: Anhydrota, 5'-dichloro-3,3'-di(γ-
sulfopropyl)-terethyl-thiacarbocyanine hydroxide pyridinium salt sensitizing dye ■: Anhydroterethyl-3,3'-cy(γ-sulfopropyl)-≠, ta, μ'-5'-dibenzothiacarbo Cyanine hydroxide/triethylamine salt sensitizing dye■:Anhydrotorethylta,! '-Dichloro-3,3'-di(γ-sulfopropyl)oxacarbocyanine sodium salt sensitizing dye ■: Anhydro-
5, Otsu, Yu/, 1/-tetrachloro-/, /'-diethyl-3,3'-di(β-[β-(r-sulfopropoxy)ethoxy]ethylimidanolocarbocyanine hydroxide sodium salt) Coupler EX-1 H EX-7 α EX-9 EX-/ θ EX-'t EX-1i H EX-/, 2 Na Example 5 On a triacetylcellulose support provided with the following layers, in the following order After coating the emulsion layer and auxiliary layer, sample jO/~!O
I got ≠.

First layer low red sensitivity emulsion layer The cyan coupler λ-(heptafluorobutyramide)-(λ'-(2''-di-t-aminophenoxy)butyramide)taenol 1009 is added to Zyl phosphate 10Occ and ethyl acetate 100
An emulsion obtained by dissolving ccK and stirring at high speed with 10 l of an aqueous solution of tizelatin. was mixed with the above red-sensitive low-iodote silver bromide emulsion / o, st7m).

2M highly red-sensitive emulsion layer cyan coupler λ-(heptafluoroduramide)-ter(z'-(2", t"-c-aminophenoxy)butyramide)-phenol l 00 fQ,
) I7 cresyl phosphate 100cc and ethyl acetate/00 CG dissolved in 10 thigelatin aqueous solution/4
The emulsion 10009 obtained by stirring at high speed was mixed with the above-mentioned red-sensitive highly iodine silver bromide emulsion (silver 702.gelatin z09).
(Iodine content: p, o mol %) and coated to a dry film thickness of 2 μm (silver amount θ, ♂2/m 2 ).

Third layer: middle layer Cottage-t-octylhydroquinone.

dibutyl phthalate) / 00 cc and ethyl acetate l
Dissolved in o o cc, aqueous solution in 10% gelatin / /
The emulsion/kg obtained by stirring at high speed with 10% gelate/K was mixed with 10% gelate/K and applied to a dry film thickness.

Hiro layer: Low green sensitivity emulsion I. A magenta coupler is used in place of the cyan coupler. /-(
2,≠,6-dolychlorophenyl)-3-(3-(,2
, Gooji-t-amylphenoxyacetamide)benzamide)-! - Emulsion 3009 obtained in the same manner as the emulsion of the first layer except for using binozolone was added to green-sensitive low-iodophilic silver bromide emulsion/9 (containing silver 702 and gelatin Otsu 09,
The iodine content is ko! Morch) and dry film thickness, θ
It was coated to give a thickness of μ (silver amount: 0.797 m ).

jN: Highly sensitive green-sensitive emulsion layer with magenta coupler instead of cyan coupler /-(
2, IA, t-trichlorophenyl)-3(3(2+≠
Emulsion 10009 obtained in the same manner as the emulsion of the first layer except that -di-t-amylphenoxyacetamido)benzamide 1-s-pyrazolone was used was converted into a green-sensitive highly iodosilver bromide emulsion. /# (Kin 70?, containing gelatin AO9, iodine content 2.0 mol%) and coated to a dry film thickness of 2.0 μm (coating forceps i0.7 f/m2).

Third layer: The emulsifier used in the third intermediate layer was mixed with 10% gelatin/4 and coated to a dry film thickness/μ.

Period 7j: Yellow filter A layer of yellow emulsion containing colloidal silver was coated to a dry film thickness/μ.

R-th layer: low-sensitivity blue-sensitivity emulsion layer An emulsion obtained in the same manner as the emulsion of the first layer except that yellow couplers of the present invention and comparative yellow couplers (specified in Table ≠) were used instead of cyan couplers. 1000 things? into a blue-sensitive, low-iodation silver bromide emulsion/'! (Contains 709 silver, 09 gelatin, and 18 iodine).

j molar ratio) and coated to a dry film thickness of 2.0 μm (coated silver amount 0, t?/m2').

7th layer: Highly sensitive blue-sensitive emulsion layer Except for using a yellow coupler (specified in Table μ, th is the same as layer) for the present invention and for comparison in place of the cyan coupler p, the first layer was Emulsion 1 obtained in the same manner as emulsion
0009 as a blue-sensitive highly iodine silver bromide emulsion/4 (silver 70f
7. Contains gelatin T09 and has iodine content! The mixture and dry film thickness (coated silver amount: 1) was coated on a morch (molch) to give a mixed-dry film thickness of θμ.

OP/m).

1st θ layer: 2nd protective layer The emulsifier l# used in the 3rd layer was mixed with 10% gelatin and coated to give a dry film thickness of 2 μm.

11th layer; 1st protective layer Fine-grain emulsion (grain size □) that has not been chemically sensitized.

/! μ, 1 mol% silver iodobromide emulsion) in a 10% gelatin aqueous solution, silver coating amount 0.3 fil/H1, dry film thickness/l
It was applied so that it became i.

The obtained film was set to 4ttroo 0 light source, and the illuminance of the exposed surface was set to 0! A color image was obtained by exposure to white light through a sensitometric wedge under 0 lux, followed by inversion as described below. The optical haze of the yellow image was measured through a blue filter.

The results are shown in Table 1.

Processing process Time Temperature First development t'3♂'c Water washing
2 l // inversion
2' 7 color development t'
〃 Adjustment −′ 〃 Bleaching J'
//Fixed 7'〃Water
Araihiro 7 7 stable
l' Regular wet/dry The following composition is used for the treatment solution.

7th developer water 70
0 Sodium tetrapolyphosphate 11um 29 Sodium subrite, 2o? Hydroquinone monosulfonate 309 Sodium carbonate (/hydrate) 302/-Phenyl t
Methyl ≠- Hydroxylmethyl-3 Pillar Zolidone
potassium dibromide
Potassium thiocyanate 7.2
9 Potassium iodide (O1/Kaya solution) ' 12m
9 Add water and make IOooml) (p
H10,/) Rebuttal liquid water 70
0rnη Nitrilo・N,N,N−)rimethyleneoschinic acid・&Na salt 32Stannic chloride (dihydrate salt)/? p-Aminephenol O1/2 Sodium hydroxide ♂2 Glacial acetic acid
/! mO.

Add water to I000mQ color developer water 70
0 strips Sodium tetrapolyphosphate, 22
Sodium chochiate 72 Sodium phosphate (/dihydrate) 3z? potassium bromide
/2 potassium iodide (θ, /
% solution) 90mQ sodium hydroxide
3g citradinic acid
/2N・Ethyl-N-(β-methanesulfonamidoethyl)-3・Methyl-guaminoaniline ・Weak electrolate salt
/ / g ethylenediamine
32 Add water 101
00O adjusted liquid water 7
00m9 Sodium nitrite /2
9 Ethylenediamine, sodium tetraacetate (dihydrate) 19 Thioglycerin 0.4tmQ glacial acetic acid
Add 3 m9 water
1000rrdL bleach solution water za00
mD.

Sodium ethylenediaminetetraacetate (dihydrate) 2.09Ethylenediaminetetraacetate iron (Ill) ammonium (dihydrate) /20.0? Potassium bromide ioo, add water -7
-10100O Fixer water 100
mQ.

Ammonium thioacrate to, oy sodium sulfite, f, 09 sodium binitrite! , 02 Add water
10100O stable liquid water g
00 +++1° formalin (37 weight section)
! , 0ml Fuji Drywell
j, OmQ add water /θ00m
From Table Q ≠ Table μ, it is clear that the coupler of the present invention has a high color density without changing fog. 1 If the color density is adjusted, the amount of coupler and/or emulsion applied can be reduced. is possible.

Patent Applicant Fuji Photo Film Co., Ltd. Procedural Amendments Showa SR October 77, 2016 Mr. Commissioner of the Patent Office 1, Indication of Case Showa! Patent Application No. 9307 2, Title of Invention Silver Halide Color Photographic Material 3
, Relationship with the case of the person making the amendment Patent applicant Address 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (520) Fuji Photo Film Co., Ltd. 4, Subject of amendment Column 5 of "Detailed Description of the Invention" of the specification, Amendment The statement in the "Detailed Description of the Invention" section of the description of contents is amended as follows.

(1) Page io, line 12 "n-tetracosyl group" "n-octadecyl group" and correct it.

(2) Page 7.2, line lψ and correct it.

(3) Page 13, line 3 and correct it.

(4) Line // from the bottom of page 22 "Sulfuryl chloride salt" "Sulfuryl chloride, salt" and correct it.

(5) 2nd ≠ page line “Cold state” "Door to door" and correct it.

<6) m’12 page 77th line After "particle size" "7.2μ, silver" Insert.

that's all

Claims (1)

[Scope of Claims] A silver halide color photographic material containing a yellow coupler represented by the following general formula (1) in at least one layer. General formula (I) represents a koxy group, an alkyl group or a carbonamide group. R4 represents an alkyl group or an alkenyl group. R5
is a nitro group, a cyan group, a carboxy group